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231.
Capillaries made of fluorinated ethylene propylene (FEP) with an inner diameter of 50 microm have been employed in capillary zone electrophoresis with UV-Vis absorbance detection. The capillaries were made in the laboratory with a recently developed technique using fluoropolymer heat shrink/melt tubing and a tungsten wire as a template for the channel. An electroosmotic flow was obtained in the channels and it is shown that an FEP capillary is more effective for a cationic test solute than a fused-silica capillary. The compatibility of FEP capillaries with optical detection is evaluated briefly. 相似文献
232.
[reaction: see text] Three novel domino reaction processes have been discovered and developed that employ the regioselective and stereoselective [Rh(CO)(2)Cl](2)-catalyzed alkylations of allylic trifluoroacetates with alpha-substituted sodiomalonates followed by an intramolecular Pauson-Khand annulation, a [5 + 2] cycloaddition, or a cycloisomerization. A unique aspect of the methodology is that a single catalyst is used to effect sequential transformations simply by increasing the temperature for the second reaction. 相似文献
233.
Stephen L. Buchwalter 《Journal of polymer science. Part A, Polymer chemistry》1985,23(12):2897-2911
The complex resins derived from furfuryl-alcohol polymerization are a result of at least four competing reactions. By converting the alcohol to its acetate ester, however, three of these reactions can be eliminated. The simpler polymer derived from furfuryl acetate has been characterized spectroscopically, and an interesting chromophoric side reaction of the polymerization has been identified. The remarkable ability of the polymer to crosslink at room temperature upon precipitation from solution is also of interest. 相似文献
234.
Stopped-flow Fourier transform infrared spectroscopy of nitromethane oxidation by the diiron(IV) intermediate of methane monooxygenase 总被引:1,自引:0,他引:1
Muthusamy M Ambundo EA George SJ Lippard SJ Thorneley RN 《Journal of the American Chemical Society》2003,125(37):11150-11151
The hydroxylase component (MMOH) of soluble methane monooxygenase from Methylococcus capsulatus (Bath) was reduced to the diiron(II) form and then allowed to react with dioxygen to generate the diiron(IV) intermediate Q in the first phase of a double-mixing stopped-flow experiment. CD3NO2 was then introduced in the second phase of the experiment, which was carried out in D2O at 25 degrees C. The kinetics of the reaction of the substrate with Q were monitored by stopped-flow Fourier transform infrared spectroscopy, observing the disappearance of the asymmetric NO2 bending vibration at 1548 cm-1. The data were fit to a single-exponential function, which yielded a kobs of 0.45 +/- 0.07 s-1. This result is in quantitative agreement with a kobs of 0.39 +/- 0.01 s-1 obtained by observing the disappearance of Q by double-mixing stopped-flow optical spectroscopy at its absorption maximum of 420 nm. These results provide for the first time direct monitoring of the hydroxylation of a methane-derived substrate in the MMOH reaction pathway and demonstrate that Q decay occurs concomitantly with substrate consumption. 相似文献
235.
Aucott SM Kilian P Milton HL Robertson SD Slawin AM Woollins JD 《Inorganic chemistry》2005,44(8):2710-2718
Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The pro-ligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp(2)TiS(2)Ar complexes (Ar = naphthalene) have been shown by temperature-dependent (1)H NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS(2)C(3) rings undergoing inversion on the NMR time scale while the similar Cp(2)TiS(2)Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO(2) groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported. 相似文献
236.
Stephen B. Colbran Brian H. Robinson Jim Simpson 《Journal of organometallic chemistry》1984,265(2):199-204
The nitrosyl clusters PPN[YCCo3(CO)7(NO)] (Y = Me, Ph, COOH, (C5H5)Fe(C5H4)) have been prepared in high yield from the reaction of YCCo3(CO)9 with PPN(NO2) in THF, acetone or acetonitrile. Spectroscopic evidence indicates the structure of the nitrosyl anions is derived from that of YCCo3(CO)9 by the replacement of two CO ligands on one cobalt atom by a linear, terminal nitrosyl group. The nitrosyl metallates are extremely sensitive to oxidation and attempts to protonate the anions resulted in the reformation of the parent YCCo3(CO)9, molecules. The oxidative electrochemistry of the ferrocene complex, PPN[(C5H5)Fe(C5H4CCo3(CO)7(NO)] is also discussed. 相似文献
237.
Stephen M. Walker 《Tetrahedron letters》2005,46(39):6611-6615
Ene cyclisation of a variety of 4-aza-1,7-dienes affords 3,4-disubstituted piperidines. In particular, cyclisation of diesters 14 and 20 catalysed by MeAlCl2 gives the corresponding trans 3,4-disubstituted piperidines with diastereomeric ratios of >200:1. 相似文献
238.
Eric W. Ainscough Tom A. James Stephen D. Robinson Jonathan N. Wingfield 《Journal of organometallic chemistry》1973,60(2):C63-C66
Osmium triphenylphosphine complexes, OsH4(PPh3)3, OsH2 (CO)(PPh3)3 and OsHCl(CO)(PPh3)3 react with triphenyl phosphite in boiling organic solvents to yield triphenyl phosphite derivatives which subsequently undergo ortho-metallation reactions. 相似文献
239.
Haiwen Zhang David W. Norman Tracey M. Wentzell Alison M. Irving Janet P. Edwards Susan L. Wheaton Christopher M. Vogels Stephen A. Westcott Felix J. Baerlocher Andreas Decken 《Transition Metal Chemistry》2005,30(1):63-68
Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na2PdCl4 afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC6H4C(O)H) with H2NC6H4Bpin (pin=1,2-O2C2Me4) afforded the boron-containing Schiff bases, 2-HOC6H4C(H)=NC6H4Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na2PdCl4 afforded complexes of the type PdL2
(4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus. 相似文献
240.